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In PCCI diesel engine, the fuel is injected much earlier than the injection timing of conventional diesel engines. Exhaust-emission improvements are attained by the lean-premixed combustion. It is expected that fuel properties influence mixture formation and combustion characteristics. In this research, experiments were carried out using a single-cylinder PCCI diesel engine operating on pure fuels with different volatilities. The injection timing and overall equivalence ratio of the premixed spray were varied. The results showed that the maximum heat release rate was smaller for lower-volatility fuel while ISFC was maintained smaller. So the combustion of a lower-volatility fuel would moderately make progress.